JP5245210B2 - Cathode active material for non-aqueous electrolyte battery and non-aqueous electrolyte battery using the same - Google Patents
Cathode active material for non-aqueous electrolyte battery and non-aqueous electrolyte battery using the same Download PDFInfo
- Publication number
- JP5245210B2 JP5245210B2 JP2006127442A JP2006127442A JP5245210B2 JP 5245210 B2 JP5245210 B2 JP 5245210B2 JP 2006127442 A JP2006127442 A JP 2006127442A JP 2006127442 A JP2006127442 A JP 2006127442A JP 5245210 B2 JP5245210 B2 JP 5245210B2
- Authority
- JP
- Japan
- Prior art keywords
- active material
- molybdenum
- positive electrode
- electrode active
- lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims description 20
- 239000006182 cathode active material Substances 0.000 title 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 68
- 229910052750 molybdenum Inorganic materials 0.000 claims description 68
- 239000011733 molybdenum Substances 0.000 claims description 68
- 239000007774 positive electrode material Substances 0.000 claims description 64
- 229910052744 lithium Inorganic materials 0.000 claims description 54
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 48
- -1 lithium transition metal Chemical class 0.000 claims description 46
- 229910052723 transition metal Inorganic materials 0.000 claims description 42
- 239000002905 metal composite material Substances 0.000 claims description 40
- 229910052712 strontium Inorganic materials 0.000 claims description 38
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 37
- 229910052759 nickel Inorganic materials 0.000 claims description 24
- 239000010941 cobalt Substances 0.000 claims description 21
- 229910017052 cobalt Inorganic materials 0.000 claims description 21
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 21
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 description 22
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 21
- 239000010937 tungsten Substances 0.000 description 21
- 229910052787 antimony Inorganic materials 0.000 description 17
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 16
- 239000011572 manganese Substances 0.000 description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 15
- 229910052748 manganese Inorganic materials 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 238000010304 firing Methods 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 12
- 238000011049 filling Methods 0.000 description 12
- 238000010828 elution Methods 0.000 description 11
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 11
- 229910000018 strontium carbonate Inorganic materials 0.000 description 11
- 239000010410 layer Substances 0.000 description 10
- 238000000634 powder X-ray diffraction Methods 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 229910016363 Ni0.33Co0.33Mn0.33O2 Inorganic materials 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000007423 decrease Effects 0.000 description 9
- 239000008151 electrolyte solution Substances 0.000 description 9
- 239000011164 primary particle Substances 0.000 description 9
- 238000004611 spectroscopical analysis Methods 0.000 description 9
- 229910016523 CuKa Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002131 composite material Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- NMHMDUCCVHOJQI-UHFFFAOYSA-N lithium molybdate Chemical compound [Li+].[Li+].[O-][Mo]([O-])(=O)=O NMHMDUCCVHOJQI-UHFFFAOYSA-N 0.000 description 6
- 239000007773 negative electrode material Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229910003002 lithium salt Inorganic materials 0.000 description 5
- 159000000002 lithium salts Chemical class 0.000 description 5
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 5
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- DUSBUJMVTRZABV-UHFFFAOYSA-M [O-2].O[Nb+4].[O-2] Chemical compound [O-2].O[Nb+4].[O-2] DUSBUJMVTRZABV-UHFFFAOYSA-M 0.000 description 1
- XIJLBSWGPVLQBE-UHFFFAOYSA-N [Sr].[Mo] Chemical compound [Sr].[Mo] XIJLBSWGPVLQBE-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
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- 229940093474 manganese carbonate Drugs 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- LNDHQUDDOUZKQV-UHFFFAOYSA-J molybdenum tetrafluoride Chemical compound F[Mo](F)(F)F LNDHQUDDOUZKQV-UHFFFAOYSA-J 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
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- 150000002816 nickel compounds Chemical class 0.000 description 1
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- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
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- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
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- 238000001556 precipitation Methods 0.000 description 1
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- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
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- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- 150000003438 strontium compounds Chemical class 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Description
本発明は、リチウムイオン二次電池等の非水電解質電池用正極活物質とそれを用いた非水電解質電池に関する。 The present invention relates to a positive electrode active material for a non-aqueous electrolyte battery such as a lithium ion secondary battery and a non-aqueous electrolyte battery using the same.
コバルト酸リチウム、ニッケル酸リチウムなどの層状構造を有するリチウム遷移金属複合酸化物は、作用電圧が４Ｖと高く、また、大きな容量が得られるため、携帯電話、ノート型パソコン、デジタルカメラ等の電子機器の電源として多く用いられている。 Lithium transition metal composite oxides having a layered structure such as lithium cobaltate and lithium nickelate have a high working voltage of 4 V and a large capacity, so that electronic devices such as mobile phones, notebook computers, digital cameras, etc. Many power sources are used.
しかしながら、現在では、電子機器の高機能化に伴い、更なる電池の高容量化が必要とされている。所定容積の電池を高容量化するためには、充填密度の高い正極活物質を正極として用いることが要望されている。 However, at the present time, with higher functionality of electronic devices, further increase in battery capacity is required. In order to increase the capacity of a battery having a predetermined volume, it is desired to use a positive electrode active material having a high packing density as a positive electrode.
そこで、本願出願人は、先の出願（特許文献１）で、モリブデン、バナジウム、タングステン、ホウ素、フッ素の少なくとも１種の化合物とリチウム原料と遷移金属原料とを混合し、焼成して得られるリチウム遷移金属複合酸化物は、充填密度の高い正極活物質であることを開示している。さらに、そのリチウム遷移金属複合酸化物を用いた電池は、負荷特性、熱安定性に優れる。 Accordingly, the applicant of the present application described in the previous application (Patent Document 1) is lithium obtained by mixing and baking at least one compound of molybdenum, vanadium, tungsten, boron, and fluorine, a lithium raw material, and a transition metal raw material. It is disclosed that the transition metal composite oxide is a positive electrode active material having a high packing density. Furthermore, a battery using the lithium transition metal composite oxide is excellent in load characteristics and thermal stability.
また、特許文献２には、熱安定性を向上させる目的で、リチウム遷移金属複合酸化物の表面に、モリブデンおよびタングステンからなる群から選ばれる少なくとも１種の元素とリチウムとを含む表面層を形成させることを開示している。そして、Ｌｉ２ＭｏＯ４粉末やＬｉ２ＷＯ４粉末で被覆処理を行うことや、リチウム遷移金属複合酸化物の原料粉末とＬｉ２ＭｏＯ４粉末とを混合して焼成することで、リチウム遷移金属複合酸化物の表面に上記表面層を形成させている。なお、特許文献２には、モリブデン、タングステンのそれぞれについて表面層を形成させることの記載はあるが、モリブデンとタングステンとを組み合わせることについては記載されていない。
In
モリブデンを含有するリチウム遷移金属複合酸化物は、充填性に優れるという特性を有する一方で、電池特性には改善の余地がある。したがって、本願発明は、充填性が良好で、電池特性にも優れる非水電解質電池用正極活物質および非水電解質電池を提供することを目的とする。 Lithium transition metal composite oxides containing molybdenum have the property of excellent filling properties, but there is room for improvement in battery characteristics. Therefore, an object of the present invention is to provide a positive electrode active material for a nonaqueous electrolyte battery and a nonaqueous electrolyte battery that have good filling properties and excellent battery characteristics.
本発明者らは鋭意検討を重ねた結果、リチウム遷移金属複合酸化物にモリブデンを含有させ、さらに、ストロンチウム、タングステン、アンチモンの少なくとも１種を含有させることによって、正極活物質の充填密度を低下させることなく、充放電サイクル特性を改善できることを見出し、本願発明を完成するに至った。 As a result of intensive investigations, the present inventors have reduced the packing density of the positive electrode active material by including molybdenum in the lithium transition metal composite oxide and further including at least one of strontium, tungsten, and antimony. Thus, the inventors have found that the charge / discharge cycle characteristics can be improved, and have completed the present invention.
本発明は、非水電解質電池に用いられる正極活物質において、前記正極活物質は、ニッケルもしくはコバルトの少なくとも１種を含有し、層状構造を有するリチウム遷移金属複合酸化物であって、前記リチウム遷移金属複合酸化物は、ストロンチウム、タングステン、アンチモンの少なくとも１種と、モリブデンと、を含有する正極活物質に関する。 The present invention relates to a positive electrode active material used in a nonaqueous electrolyte battery, wherein the positive electrode active material is a lithium transition metal composite oxide containing at least one of nickel and cobalt and having a layered structure, The metal composite oxide relates to a positive electrode active material containing at least one of strontium, tungsten, and antimony and molybdenum.
前記リチウム遷移金属複合酸化物は、少なくともニッケルとコバルトとを含有することが好ましい。 The lithium transition metal composite oxide preferably contains at least nickel and cobalt.
前記リチウム遷移金属複合酸化物は、少なくともニッケルとコバルトとマンガンとを含有することが好ましい。 The lithium transition metal composite oxide preferably contains at least nickel, cobalt, and manganese.
前記モリブデンの含有量は、前記リチウム遷移金属複合酸化物に対して、０ｍｏｌ％より大きく２．０ｍｏｌ％以下であることが好ましい。 The molybdenum content is preferably greater than 0 mol% and less than or equal to 2.0 mol% with respect to the lithium transition metal composite oxide.
前記モリブデンの含有量に対する前記ストロンチウム、タングステン、アンチモンの少なくとも１種の含有量の比率は、モル比で、０より大きく３．０以下であることことが好ましい。 The ratio of the content of at least one of strontium, tungsten, and antimony to the content of molybdenum is preferably greater than 0 and 3.0 or less in terms of molar ratio.
また、本発明は、上記リチウム遷移金属複合酸化物を用いた非水電解質電池に関する。 The present invention also relates to a nonaqueous electrolyte battery using the lithium transition metal composite oxide.
本発明は、以上に説明したように構成されているので、充填性に優れる正極活物質とすることができるとともに、その正極活物質を用いた電池は、サイクル特性にも優れる。 Since the present invention is configured as described above, it can be a positive electrode active material excellent in filling properties, and a battery using the positive electrode active material is also excellent in cycle characteristics.
以下、本発明について更に詳しく説明する。だたし、本発明は、この実施の形態及び実施例に限定されない。
〔層状構造のリチウム遷移金属複合酸化物〕
本発明に用いる層状構造を有するリチウム遷移金属複合酸化物（以下、正極活物質と言うこともある。）としては、一般式：Ｌｉ１＋γＮｉｘＭｎｙＣｏ１−ｘ−ｙＯ２・ＭｏａＭｂ（但し、ＭはＳｒ、Ｗ、Ｓｂのうち少なくとも１種の元素であり、γ、ｘ、ｙ、ａ、ｂは、０＜γ≦０．５、０．３≦ｘ≦１．０、０≦ｙ≦０．７、０＜ａ≦０．０２、０＜ｂ≦３．０ａを満足する。）で表すものを用いることができる。
Hereinafter, the present invention will be described in more detail. However, the present invention is not limited to this embodiment and example.
[Lithium transition metal composite oxide with layered structure]
The lithium transition metal composite oxide having a layered structure used in the present invention (hereinafter sometimes referred to as a positive electrode active material) has a general formula: Li 1 + γ Ni x Mn y Co 1-xy O 2 · Mo a M b (where M is at least one element of Sr, W, and Sb, and γ, x, y, a, and b are 0 <γ ≦ 0.5, 0.3 ≦ x ≦ 1.0, respectively. , 0 ≦ y ≦ 0.7, 0 <a ≦ 0.02, and 0 <b ≦ 3.0a).
本発明の正極活物質は充填性に優れるため、本発明の正極活物質を電池に用いることで高容量化が可能である。本発明の正極活物質が充填性に優れる理由は、リチウム遷移金属複合酸化物にモリブデンを含有させるところにある。モリブデンは、その化合物とリチウム遷移金属複合酸化物の原料とともに混合され焼成される。モリブデンは、リチウム遷移金属複合酸化物の粒成長を促進させるフラックス剤として用いられる一方で、リチウム遷移金属複合酸化物の一次粒子の形状を球状に成長させる作用も有する。ここで、一次粒子とは、粉末を形成する最も小さい粒子のことを言う。通常、リチウム遷移金属複合酸化物は、一次粒子と一次粒子が複数集合して形成された二次粒子とからなる粒子の形態で存在するが、一次粒子が球状であると、正極作製工程におけるロールプレス成形時に、一次粒子の移動がなめらかに行われるため、二次粒子の隙間に一次粒子が充填されやすい。したがって、モリブデンを含有する正極活物質は、充填性に優れる粒子であるため、集電体上の正極活物質層中に含まれる正極活物質を高密度に形成することができる。 Since the positive electrode active material of the present invention is excellent in fillability, the capacity can be increased by using the positive electrode active material of the present invention for a battery. The reason why the positive electrode active material of the present invention is excellent in filling property is that the lithium transition metal composite oxide contains molybdenum. Molybdenum is mixed and fired together with the compound and the raw material of the lithium transition metal composite oxide. Molybdenum is used as a fluxing agent that promotes the grain growth of the lithium transition metal composite oxide, and also has the effect of growing the shape of the primary particles of the lithium transition metal composite oxide into a spherical shape. Here, primary particles refer to the smallest particles that form a powder. Usually, the lithium transition metal composite oxide exists in the form of particles composed of primary particles and secondary particles formed by aggregating a plurality of primary particles, but if the primary particles are spherical, the roll in the positive electrode preparation step Since the primary particles move smoothly during press molding, the primary particles are easily filled in the gaps between the secondary particles. Therefore, since the positive electrode active material containing molybdenum is a particle having excellent filling properties, the positive electrode active material contained in the positive electrode active material layer on the current collector can be formed with high density.
しかし、モリブデンのみを含有するリチウム遷移金属複合酸化物は、充填性に優れるという特性を有するが、サイクル特性については改善の余地がある。モリブデンのみを含有するリチウム遷移金属複合酸化物の場合、モリブデンはモリブデン酸リチウム（Ｌｉ２ＭｏＯ４）として正極活物質に存在するが、このモリブデン酸リチウムは、電解液に溶出しやすい化合物である。そのため、モリブデン酸リチウムは、充放電サイクル時に、正極活物質から電解液へ溶出し、さらには、負極へ析出する。詳細な劣化機構は定かではないが、このモリブデンの溶出および析出が、サイクル特性に悪影響を及ぼすと考えられている。 However, a lithium transition metal composite oxide containing only molybdenum has a characteristic of excellent filling properties, but there is room for improvement in cycle characteristics. In the case of a lithium transition metal composite oxide containing only molybdenum, molybdenum is present in the positive electrode active material as lithium molybdate (Li 2 MoO 4 ), but this lithium molybdate is a compound that easily elutes into the electrolyte. Therefore, lithium molybdate elutes from the positive electrode active material to the electrolyte during the charge / discharge cycle, and further deposits on the negative electrode. Although the detailed degradation mechanism is not clear, it is thought that this elution and precipitation of molybdenum adversely affects the cycle characteristics.
そこで、モリブデンと、さらに、ストロンチウム、タングステン、アンチモンの少なくとも１種をリチウム遷移金属複合酸化物に含有させることで、本発明の正極活物質は、モリブデンの電解液への溶出を抑制することができる。これは、リチウム遷移金属複合酸化物の製造工程における焼成時に、モリブデンと上記元素とが反応して、モリブデンと上記元素の複合化合物またはリチウムとモリブデンと上記元素との複合化合物となるため、電解液に溶出しやすいモリブデン酸リチウムの生成を抑制するとともに、上記複合化合物自体も電解液に溶出しにくいためである。したがって、本発明の正極活物質は、モリブデンのみを含有する場合よりも、モリブデンが電解液へ溶出するのを抑制することができ、その結果、サイクル特性を改善することができる。 Therefore, the positive electrode active material of the present invention can suppress elution of molybdenum into the electrolytic solution by containing molybdenum and at least one of strontium, tungsten, and antimony in the lithium transition metal composite oxide. . This is because molybdenum and the above element react to form a composite compound of molybdenum and the above element or a composite compound of lithium, molybdenum and the above element during firing in the manufacturing process of the lithium transition metal composite oxide. This is because the generation of lithium molybdate that easily elutes into the electrolyte is suppressed, and the composite compound itself is also difficult to elute into the electrolyte. Therefore, the positive electrode active material of the present invention can suppress the elution of molybdenum into the electrolytic solution as compared with the case of containing only molybdenum, and as a result, the cycle characteristics can be improved.
さらに、ストロンチウム、タングステン、アンチモンの少なくとも１種は、一次粒子を球状に成長させるというモリブデンの作用を大きく阻害することはない。したがって、本発明は、ストロンチウム、タングステン、アンチモンの少なくとも１種と、モリブデンとをリチウム遷移金属複合酸化物に含有させることで、充填性およびサイクル特性に優れる正極活物質および電池とすることができる。 Furthermore, at least one of strontium, tungsten, and antimony does not significantly inhibit the action of molybdenum that grows primary particles into a spherical shape. Therefore, according to the present invention, a positive electrode active material and a battery excellent in filling property and cycle characteristics can be obtained by including at least one of strontium, tungsten, and antimony and molybdenum in the lithium transition metal composite oxide.
本発明に用いる層状構造を有するリチウム遷移金属複合酸化物は、ニッケルを含んでいることが好ましく、これにより、高い容量を示す正極活物質とすることができる。また、モリブデンのフラックス作用及び一次粒子を球状に成長させるという作用は、コバルト酸リチウムやマンガン酸リチウム等のリチウム遷移金属複合酸化物の中でも、特に、ニッケルを含む層状のリチウム遷移金属複合酸化物に対して顕著である。さらに、本発明の正極活物質は、サイクル特性を向上させるために、ニッケルに加えてコバルトを含んでいることが好ましい。さらには、マンガンを含んでいることがより好ましく、これにより熱安定性を向上させることができる。 The lithium transition metal composite oxide having a layered structure used in the present invention preferably contains nickel, whereby a positive electrode active material exhibiting a high capacity can be obtained. In addition, the flux of molybdenum and the action of growing primary particles into a spherical shape are particularly effective for layered lithium transition metal composite oxides containing nickel among lithium transition metal composite oxides such as lithium cobaltate and lithium manganate. It is remarkable for this. Furthermore, the positive electrode active material of the present invention preferably contains cobalt in addition to nickel in order to improve cycle characteristics. Furthermore, it is more preferable that manganese is contained, and this can improve thermal stability.
本発明の正極活物質は、モリブデンの含有量が、リチウム遷移金属複合酸化物に対して、０ｍｏｌ％より大きく２ｍｏｌ％以下であることが好ましい。０．１ｍｏｌ％以上であるのがより好ましく、また、１．５ｍｏｌ以下であるのがより好ましい。モリブデンの含有量が多すぎると、充放電容量が低下する。モリブデンの含有量が少なすぎると、正極活物質の充填性が向上しない。 In the positive electrode active material of the present invention, the molybdenum content is preferably greater than 0 mol% and not greater than 2 mol% with respect to the lithium transition metal composite oxide. The amount is more preferably 0.1 mol% or more, and more preferably 1.5 mol or less. When there is too much content of molybdenum, charging / discharging capacity will fall. When there is too little content of molybdenum, the filling property of a positive electrode active material will not improve.
さらに、本発明の正極活物質は、モリブデンの含有量に対するストロンチウム、タングステン、アンチモンの少なくとも１種の含有量の比率は、モル比で、０より大きく３．０以下であることが好ましい。０．５以上であるのがより好ましく、また、２．０以下であるのがより好ましい。モリブデンの含有量に対するストロンチウム、タングステン、アンチモンの少なくとも１種の含有量が多すぎると、充填性はそれほど向上せず、充放電容量も低下する。モリブデンの含有量に対するストロンチウム、タングステン、アンチモンの少なくとも１種の含有量が少なすぎると、モリブデンの溶出を抑制する効果は小さく、サイクル特性はあまり向上されない。
〔層状構造のリチウム遷移金属複合酸化物の製造方法〕
本発明の層状構造のリチウム遷移金属複合酸化物の原料には、各元素の酸化物、水酸化物、硝酸塩、硫酸塩、炭酸塩等を用いることができる。例えば、リチウム源としては、炭酸リチウム、硝酸リチウム、水酸化リチウム等を挙げることができる。ニッケル源としては、炭酸ニッケル、硫酸ニッケル、水酸化ニッケル、酸化ニッケル、過酸化ニッケル等を挙げることができる。マンガン源としては、二酸化マンガン、三酸化ニマンガン、四酸化三マンガン、炭酸マンガン、硝酸マンガン、硫酸マンガン等を挙げることができる。コバルト源としては、酸化コバルト、三酸化ニコバルト、四酸化三コバルト、水酸化コバルト、硝酸コバルト、硫酸コバルト等を挙げることができる。
Furthermore, in the positive electrode active material of the present invention, the ratio of the content of at least one of strontium, tungsten, and antimony to the molybdenum content is preferably greater than 0 and 3.0 or less in terms of molar ratio. More preferably, it is 0.5 or more, and more preferably 2.0 or less. If the content of at least one of strontium, tungsten, and antimony with respect to the molybdenum content is too large, the filling property is not improved so much and the charge / discharge capacity is also reduced. If the content of at least one of strontium, tungsten, and antimony with respect to the molybdenum content is too small, the effect of suppressing the elution of molybdenum is small, and the cycle characteristics are not so improved.
[Method of producing layered lithium transition metal composite oxide]
As the raw material of the lithium transition metal composite oxide having a layered structure of the present invention, oxides, hydroxides, nitrates, sulfates, carbonates, and the like of each element can be used. For example, examples of the lithium source include lithium carbonate, lithium nitrate, and lithium hydroxide. Examples of the nickel source include nickel carbonate, nickel sulfate, nickel hydroxide, nickel oxide, nickel peroxide and the like. Examples of manganese sources include manganese dioxide, nimanganese trioxide, trimanganese tetroxide, manganese carbonate, manganese nitrate, and manganese sulfate. Examples of the cobalt source include cobalt oxide, niobium trioxide, tricobalt tetroxide, cobalt hydroxide, cobalt nitrate, and cobalt sulfate.
また、リチウム遷移金属複合酸化物に、例えば、ニッケル−コバルトまたはニッケル−マンガン−コバルトのように２種以上の遷移金属元素を含有させる場合、上述したニッケル、マンガン、コバルトのそれぞれの化合物とリチウム化合物とを混合焼成して作製することも可能である。一方で、ニッケル、マンガン、コバルトのそれぞれの化合物を、同一容器に溶解させた後、沈殿剤を投下することで作製されるニッケル−コバルトまたはニッケル−マンガン−コバルトからなる炭酸塩や水酸化物などを原料として用いることもできる。 In addition, when two or more transition metal elements such as nickel-cobalt or nickel-manganese-cobalt are included in the lithium transition metal composite oxide, the above-mentioned compounds of nickel, manganese, and cobalt and lithium compounds described above It is also possible to produce by mixing and firing. On the other hand, after dissolving each compound of nickel, manganese, and cobalt in the same container, the carbonate, hydroxide, etc. which consist of nickel-cobalt or nickel-manganese-cobalt produced by dropping a precipitant Can also be used as a raw material.
モリブデン源として、例えば、酸化モリブデン、モリブデン酸リチウム、塩化モリブデン、フッ化モリブデン、モリブデン酸アンモニウム等が挙げられる。なかでも、酸化モリブデンが好ましい。ストロンチウム源としては、酸化ストロンチウム、炭酸ストロンチウム、硝酸ストロンチウム、塩化ストロンチウム等が挙げられる。なかでも、コストの面から炭酸ストロンチウムが好ましい。タングステン源としては、酸化タングステン、六塩化タングステン等が挙げられる。なかでも、酸化タングステンが好ましい。アンチモンとしては、五酸化アンチモン、三酸化アンチモン、五塩化アンチモン、三塩化アンチモン等が挙げられる。なかでも、酸化アンチモンが好ましい。 Examples of the molybdenum source include molybdenum oxide, lithium molybdate, molybdenum chloride, molybdenum fluoride, and ammonium molybdate. Of these, molybdenum oxide is preferable. Examples of the strontium source include strontium oxide, strontium carbonate, strontium nitrate, and strontium chloride. Of these, strontium carbonate is preferable from the viewpoint of cost. Examples of the tungsten source include tungsten oxide and tungsten hexachloride. Of these, tungsten oxide is preferable. Examples of antimony include antimony pentoxide, antimony trioxide, antimony pentachloride, and antimony trichloride. Of these, antimony oxide is preferable.
例えば、遷移金属元素としてニッケル、マンガン、コバルトを含有し、さらに、モリブデンとストロンチウムとを含有するリチウム遷移金属複合酸化物を作製する場合、以下のような工程によって得ることができる。 For example, when a lithium transition metal composite oxide containing nickel, manganese, and cobalt as a transition metal element and further containing molybdenum and strontium is produced, it can be obtained by the following steps.
上述したニッケル化合物、マンガン化合物、コバルト化合物から調製した所定の組成比のコバルトイオン、ニッケルイオン、マンガンイオンを含有する水溶液を、攪拌している純水中に滴下する。さらに、水溶液温度を４０〜８０℃とし、水溶液を攪拌しながら、水溶液がｐＨ８〜１１となるように水酸化ナトリウム水溶液を滴下することで、コバルト−ニッケル−マンガンの沈殿物が得られる。なお、水酸化ナトリウム水溶液の代わりに、炭酸水素アンモニウム水溶液、炭酸水素ナトリウム水溶液、水酸化カリウム水溶液、水酸化リチウム水溶液等のアルカリ溶液を用いることもできる。 An aqueous solution containing cobalt ions, nickel ions, and manganese ions having a predetermined composition ratio prepared from the nickel compound, manganese compound, and cobalt compound described above is dropped into pure water that is being stirred. Furthermore, the aqueous solution temperature is set to 40 to 80 ° C., and while stirring the aqueous solution, a sodium hydroxide aqueous solution is dropped so that the aqueous solution has a pH of 8 to 11, whereby a cobalt-nickel-manganese precipitate is obtained. Instead of the sodium hydroxide aqueous solution, an alkaline solution such as an ammonium hydrogen carbonate aqueous solution, a sodium hydrogen carbonate aqueous solution, a potassium hydroxide aqueous solution, or a lithium hydroxide aqueous solution can also be used.
つぎに、水溶液をろ過して沈殿物を採取し、採取した沈殿物を水洗し、熱処理した後、上述したリチウム化合物、モリブデン化合物、ストロンチウム化合物とを混合して、原料混合物を得る。モリブデン、ストロンチウムの添加方法は、上記方法に限定されず、次工程の焼成の前であれば、いずれの時点で行われてもよい。例えば、上記コバルト−ニッケル−マンガンの沈殿物に、さらにモリブデン、ストロンチウムの少なくとも１種を含有させた沈殿物を用いて原料混合物とすることができる。 Next, the aqueous solution is filtered to collect a precipitate. The collected precipitate is washed with water and heat-treated, and then the above-described lithium compound, molybdenum compound, and strontium compound are mixed to obtain a raw material mixture. The addition method of molybdenum and strontium is not limited to the above method, and may be performed at any time as long as it is before firing in the next step. For example, a raw material mixture can be obtained by using a precipitate in which at least one of molybdenum and strontium is further added to the cobalt-nickel-manganese precipitate.
ついで、原料混合物を焼成する。焼成の温度、時間、雰囲気等は、特に限定されず、目的に応じて適宜決定することができる。 Next, the raw material mixture is fired. The firing temperature, time, atmosphere, and the like are not particularly limited, and can be appropriately determined according to the purpose.
焼成温度は、８００℃以上であるのが好ましい。焼成温度が低すぎると、未反応の原料が正極活物質中に残留し、単位重量当たりの放電容量の低下、サイクル特性の低下、作動電圧の低下を招く。また、焼成温度は、１１００℃以下であるのが好ましい。焼成温度が高すぎると、副生成物が生成しやすくなり、単位重量当たりの放電容量の低下、サイクル特性の低下、作動電圧の低下を招く。焼成の時間は、５時間以上であるのが好ましい。上記範囲であると、混合物の粒子間の拡散反応が十分に進行する。また、焼成の時間は、３０時間以下であるのが好ましい。上記範囲であると、生産性に優れる。 The firing temperature is preferably 800 ° C. or higher. If the firing temperature is too low, unreacted raw materials remain in the positive electrode active material, resulting in a decrease in discharge capacity per unit weight, a decrease in cycle characteristics, and a decrease in operating voltage. Moreover, it is preferable that a calcination temperature is 1100 degrees C or less. If the firing temperature is too high, by-products are likely to be generated, resulting in a decrease in discharge capacity per unit weight, a decrease in cycle characteristics, and a decrease in operating voltage. The firing time is preferably 5 hours or longer. Within the above range, the diffusion reaction between the particles of the mixture proceeds sufficiently. The firing time is preferably 30 hours or less. Within the above range, productivity is excellent.
焼成の雰囲気は、例えば、大気、酸素ガス、これらと窒素ガス、アルゴンガス等の不活性ガスとの混合ガス、酸素濃度（酸素分圧）を制御した雰囲気、弱酸化雰囲気が挙げられる。 Examples of the firing atmosphere include air, oxygen gas, a mixed gas of these with an inert gas such as nitrogen gas and argon gas, an atmosphere in which the oxygen concentration (oxygen partial pressure) is controlled, and a weak oxidizing atmosphere.
焼成後、所望により、らいかい乳鉢、ボールミル、振動ミル、ピンミル、ジェットミル等を用いて粉砕し、目的とする粒度の粉体とすることもできる。
〔正極〕
正極は、リチウム遷移金属複合酸化物、導電材及び結着剤を含有する正極活物質層を集電体上に形成してなるものである。
After firing, if desired, the powder may be pulverized using a rough mortar, ball mill, vibration mill, pin mill, jet mill or the like to obtain a powder having a desired particle size.
[Positive electrode]
The positive electrode is formed by forming a positive electrode active material layer containing a lithium transition metal composite oxide, a conductive material and a binder on a current collector.
正極活物質層は、通常、正極活物質と結着剤と導電材とを液体媒体中に分散させてスラリー状にして、正極集電体に塗布、乾燥することにより作成される。さらに、塗布、乾燥によって得られた正極活物質層は、正極活物質の充填密度を上げるために、ロールプレス機等により加圧される。 The positive electrode active material layer is usually prepared by dispersing a positive electrode active material, a binder, and a conductive material in a liquid medium to form a slurry, which is applied to a positive electrode current collector and dried. Furthermore, the positive electrode active material layer obtained by coating and drying is pressurized by a roll press machine or the like in order to increase the packing density of the positive electrode active material.
正極集電体の材質としては、アルミニウムが好ましい。 The material for the positive electrode current collector is preferably aluminum.
正極活物質層の製造に用いる結着剤としては、特に限定されず、例えば、ポリフッ化ビニリデン、ポリテトラフルオロエチレン、ポリアミドアクリル樹脂等が挙げられる。 The binder used for manufacturing the positive electrode active material layer is not particularly limited, and examples thereof include polyvinylidene fluoride, polytetrafluoroethylene, and polyamide acrylic resin.
正極活物質層には、通常、導電性を高めるために導電材を含有させる。その種類に特に制限はないが、天然黒鉛、人造黒鉛等の黒鉛（グラファイト）、アセチレンブラック等のカーボンブラック等の炭素材料などを挙げることができる。なお、これらの物質は、１種を単独で用いても良く、２種以上を併用しても良い。
〔非水電解質電池〕
本発明の非水電解質電池は、本発明の正極活物質を用いた正極と、リチウムを吸蔵・放出可能な負極と、リチウム塩を電解質とする非水電解質とを備える。更に、正極と負極との間に、非水電解質を保持するセパレータを備える。
The positive electrode active material layer usually contains a conductive material in order to increase conductivity. Although there is no restriction | limiting in particular in the kind, Carbon materials, such as graphite (graphite), such as natural graphite and artificial graphite, carbon black, such as acetylene black, etc. can be mentioned. In addition, these substances may be used individually by 1 type, and may use 2 or more types together.
[Nonaqueous electrolyte battery]
The nonaqueous electrolyte battery of the present invention includes a positive electrode using the positive electrode active material of the present invention, a negative electrode capable of inserting and extracting lithium, and a nonaqueous electrolyte using a lithium salt as an electrolyte. Furthermore, a separator for holding a nonaqueous electrolyte is provided between the positive electrode and the negative electrode.
負極は通常、正極と同様に、負極集電体上に負極活物質層を形成して構成される。 The negative electrode is usually configured by forming a negative electrode active material layer on a negative electrode current collector, similarly to the positive electrode.
負極活物質としては、金属リチウム、リチウムアルミニウム合金等のリチウム合金、リチウムの吸蔵及び放出が可能な炭素材料が挙げられる。通常は安全性の高さの面から、リチウムを吸蔵、放出できる炭素材料が用いられる。例えば、天然黒鉛等の黒鉛（グラファイト）、人造黒鉛が挙げられる。 Examples of the negative electrode active material include lithium alloys such as metallic lithium and lithium aluminum alloy, and carbon materials capable of inserting and extracting lithium. Usually, a carbon material capable of inserting and extracting lithium is used from the viewpoint of high safety. Examples thereof include graphite such as natural graphite and artificial graphite.
なお、上述の炭素材料の他に、リチウムの吸蔵及び放出が可能な化合物を負極活物質として用いることもできる。例えば、酸化錫や酸化チタン等の金属酸化物が挙げられる。 In addition to the carbon material described above, a compound capable of inserting and extracting lithium can be used as the negative electrode active material. Examples thereof include metal oxides such as tin oxide and titanium oxide.
電解質としては、作動電圧で変質したり、分解したりしない化合物であれば特に限定されない。電解質には、電解液も含まれる。電解液の溶媒としては、例えば、ジメトキシエタン、ジエトキシエタン、エチレンカーボネート、プロピレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、メチルエチルカーボネート、メチルホルメート、γ−ブチロラクトン、２−メチルテトラヒドロフラン、ジメチルスルホキシド、スルホラン等の有機溶媒が挙げられる。これらは単独または２種類以上を混合して用いることができる。 The electrolyte is not particularly limited as long as it is a compound that is not altered or decomposed by the operating voltage. The electrolyte includes an electrolytic solution. Examples of the solvent for the electrolytic solution include dimethoxyethane, diethoxyethane, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl formate, γ-butyrolactone, 2-methyltetrahydrofuran, dimethyl sulfoxide, sulfolane and the like. These organic solvents are mentioned. These can be used alone or in admixture of two or more.
電解液のリチウム塩としては、例えば、過塩素酸リチウム、四フッ化ホウ酸リチウム、六フッ化リン酸リチウム、トリフルオロメタン酸リチウム等のリチウム塩が挙げられる。上述した溶媒とリチウム塩とを混合して電解液とする。ここで、ゲル化剤等を添加し、ゲル状として使用してもよい。また、吸液性を有するポリマーに吸収させて使用してもよい。リチウム塩は電解液中に、通常０．５ｍｏｌ／Ｌ以上１．５ｍｏｌ／Ｌ以下となるように含有させる。 Examples of the lithium salt of the electrolytic solution include lithium salts such as lithium perchlorate, lithium tetrafluoroborate, lithium hexafluorophosphate, and lithium trifluoromethanoate. The above-described solvent and lithium salt are mixed to obtain an electrolytic solution. Here, a gelling agent or the like may be added and used as a gel. Moreover, you may make it absorb and use for the polymer which has a liquid absorptivity. The lithium salt is usually contained in the electrolyte so as to be 0.5 mol / L or more and 1.5 mol / L or less.
更に、無機系または有機系のリチウムイオンの導電性を有する固体電解質を使用してもよい。 Further, a solid electrolyte having conductivity of inorganic or organic lithium ions may be used.
セパレータとしては、ポリエチレン、ポリプロピレン等の多孔性膜が挙げられる。 Examples of the separator include porous films such as polyethylene and polypropylene.
本発明の非水電解質電池は、本発明の正極活物質を用いた正極と、負極と、電解質と、必要に応じて用いられるセパレータとを、適切な形状に組み立てることにより製造される。更に、必要に応じて外装ケース等の他の構成要素を用いることも可能である。 The nonaqueous electrolyte battery of the present invention is manufactured by assembling a positive electrode using the positive electrode active material of the present invention, a negative electrode, an electrolyte, and a separator used as necessary into an appropriate shape. Furthermore, other components such as an outer case can be used as necessary.
以下、本発明の実施例を具体的に説明するが、本発明はこれらに限られるものではない。
（１）正極活物質の作製
＜実施例１＞
反応槽に、硫酸コバルト、硫酸ニッケル、硫酸マンガンから調製したコバルトイオン、ニッケルイオン、マンガンイオンを含有する水溶液を用意する。水溶液中のコバルト、ニッケル、マンガンのモル比（コバルト：ニッケル：マンガン）は、１：１：１となるように調整する。水溶液温度を６５℃にし、水溶液を攪拌しながら水酸化ナトリウム水溶液を一定量滴下する。これにより、コバルト、ニッケルおよびマンガンを沈殿させ、コバルト−ニッケル−マンガン複合水酸化物からなる沈殿物を得る。得られた沈殿物をろ過、水洗、熱処理後、炭酸リチウム、酸化モリブデン（ＭｏＯ３）、炭酸ストロンチウム（ＳｒＣＯ３）とを混合する。炭酸リチウムは、コバルト、ニッケル、マンガンのモル総和に対してリチウムのモル比を１．０２となるように調整する。酸化モリブデンは、コバルト、ニッケル、マンガンのモル総和に対してモリブデンのモル比を０．０１となるように調整する。炭酸ストロンチウムは、コバルト、ニッケル、マンガンのモル総和に対してストロンチウムのモル比を０．０１となるように調整する。混合後、大気中にて９５０℃で１５時間焼成する。
Examples of the present invention will be specifically described below, but the present invention is not limited to them.
(1) Preparation of positive electrode active material <Example 1>
An aqueous solution containing cobalt ions, nickel ions, and manganese ions prepared from cobalt sulfate, nickel sulfate, and manganese sulfate is prepared in a reaction vessel. The molar ratio of cobalt, nickel and manganese in the aqueous solution (cobalt: nickel: manganese) is adjusted to 1: 1: 1. The aqueous solution temperature is set to 65 ° C., and a certain amount of aqueous sodium hydroxide solution is added dropwise while stirring the aqueous solution. Thereby, cobalt, nickel, and manganese are precipitated, and the deposit which consists of a cobalt-nickel-manganese composite hydroxide is obtained. The obtained precipitate is filtered, washed with water, and heat treated, and then mixed with lithium carbonate, molybdenum oxide (MoO 3 ), and strontium carbonate (SrCO 3 ). Lithium carbonate is adjusted so that the molar ratio of lithium is 1.02 with respect to the total molar amount of cobalt, nickel, and manganese. Molybdenum oxide is adjusted so that the molar ratio of molybdenum is 0.01 with respect to the total molar amount of cobalt, nickel, and manganese. Strontium carbonate is adjusted so that the molar ratio of strontium is 0.01 with respect to the total molar amount of cobalt, nickel and manganese. After mixing, it is fired at 950 ° C. for 15 hours in the air.
焼成後粉砕する。得られた正極活物質の組成は、ＩＣＰ発光分光分析の結果、Ｌｉ１．０２Ｎｉ０．３３Ｃｏ０．３３Ｍｎ０．３３Ｏ２・Ｍｏ０．０１Ｓｒ０．０１である。 Grind after firing. The composition of the obtained positive electrode active material is Li 1.02 Ni 0.33 Co 0.33 Mn 0.33 O 2 .Mo 0.01 Sr 0.01 as a result of ICP emission spectroscopic analysis.
また、ＣｕＫａ線を使用した粉体Ｘ線回折からは、ＳｒＭｏＯ４の存在が確認できる。 The presence of SrMoO 4 can be confirmed from powder X-ray diffraction using CuKa line.
＜比較例１＞
炭酸ストロンチウムを、コバルト、ニッケル、マンガンのモル総和に対してストロンチウムのモル比が０．００２５となるように調整する以外は、実施例１と同様の方法で正極活物質を得る。得られた正極活物質の組成は、ＩＣＰ発光分光分析の結果、Ｌｉ１．０２Ｎｉ０．３３Ｃｏ０．３３Ｍｎ０．３３Ｏ２・Ｍｏ０．０１Ｓｒ０．００２５である。
< Comparative Example 1 >
A positive electrode active material is obtained in the same manner as in Example 1 except that strontium carbonate is adjusted so that the molar ratio of strontium to the total molar amount of cobalt, nickel, and manganese is 0.0025. The composition of the obtained positive electrode active material is Li 1.02 Ni 0.33 Co 0.33 Mn 0.33 O 2 .Mo 0.01 Sr 0.0025 as a result of ICP emission spectroscopic analysis.
また、ＣｕＫａ線を使用した粉体Ｘ線回折からは、ＳｒＭｏＯ４の存在が確認できる。 The presence of SrMoO 4 can be confirmed from powder X-ray diffraction using CuKa line.
＜実施例２＞
炭酸ストロンチウムを、コバルト、ニッケル、マンガンのモル総和に対してストロンチウムのモル比が０．００５となるように調整する以外は、実施例１と同様の方法で正極活物質を得る。得られた正極活物質の組成は、ＩＣＰ発光分光分析の結果、Ｌｉ１．０２Ｎｉ０．３３Ｃｏ０．３３Ｍｎ０．３３Ｏ２・Ｍｏ０．０１Ｓｒ０．００５である。
<Example 2 >
A positive electrode active material is obtained in the same manner as in Example 1 except that strontium carbonate is adjusted so that the molar ratio of strontium to the total molar amount of cobalt, nickel, and manganese is 0.005. The composition of the obtained positive electrode active material is Li 1.02 Ni 0.33 Co 0.33 Mn 0.33 O 2 .Mo 0.01 Sr 0.005 as a result of ICP emission spectroscopic analysis.
また、ＣｕＫａ線を使用した粉体Ｘ線回折からは、ＳｒＭｏＯ４の存在が確認できる。 The presence of SrMoO 4 can be confirmed from powder X-ray diffraction using CuKa line.
＜実施例３＞
炭酸ストロンチウムを、コバルト、ニッケル、マンガンのモル総和に対してストロンチウムのモル比が０．０２となるように調整する以外は、実施例１と同様の方法で正極活物質を得る。得られた正極活物質の組成は、ＩＣＰ発光分光分析の結果、Ｌｉ１．０２Ｎｉ０．３３Ｃｏ０．３３Ｍｎ０．３３Ｏ２・Ｍｏ０．０１Ｓｒ０．０２である。
<Example 3 >
A positive electrode active material is obtained in the same manner as in Example 1 except that strontium carbonate is adjusted so that the molar ratio of strontium to the total molar amount of cobalt, nickel, and manganese is 0.02. The composition of the obtained positive electrode active material is Li 1.02 Ni 0.33 Co 0.33 Mn 0.33 O 2 .Mo 0.01 Sr 0.02 as a result of ICP emission spectroscopic analysis.
また、ＣｕＫａ線を使用した粉体Ｘ線回折からは、ＬｉＳｒ２ＭｏＯ５．５の存在が確認できる。 The presence of LiSr 2 MoO 5.5 can be confirmed from powder X-ray diffraction using CuKa line.
＜比較例２＞
炭酸ストロンチウムの代わりに酸化タングステン（ＷＯ３）とし、酸化タングステンを、コバルト、ニッケル、マンガンのモル総和に対してタングステンのモル比が０．００２５となるように調整する以外は、実施例１と同様の方法で正極活物質を得る。得られた正極活物質の組成は、ＩＣＰ発光分光分析の結果、Ｌｉ１．０２Ｎｉ０．３３Ｃｏ０．３３Ｍｎ０．３３Ｏ２・Ｍｏ０．０１Ｗ０．００２５である。
< Comparative example 2 >
Example 1 except that tungsten oxide (WO 3 ) is used instead of strontium carbonate, and the tungsten oxide is adjusted so that the molar ratio of tungsten to the total molar amount of cobalt, nickel, and manganese is 0.0025. The positive electrode active material is obtained by this method. The composition of the obtained positive electrode active material is Li 1.02 Ni 0.33 Co 0.33 Mn 0.33 O 2 .Mo 0.01 W 0.0025 as a result of ICP emission spectroscopic analysis.
また、ＣｕＫａ線を使用した粉体Ｘ線回折では、タングステンのピークは検出されないが、タングステンはアモルファスの状態で存在していると考えられる。 Further, in the powder X-ray diffraction using CuKa line, no tungsten peak is detected, but it is considered that tungsten exists in an amorphous state.
＜比較例３＞
炭酸ストロンチウムの代わりに酸化アンチモン（Ｓｂ２Ｏ３）とし、酸化アンチモンを、コバルト、ニッケル、マンガンのモル総和に対してアンチモンのモル比が０．００５となるように調整する以外は、実施例１と同様の方法で正極活物質を得る。得られた正極活物質の組成は、ＩＣＰ発光分光分析の結果、Ｌｉ１．０２Ｎｉ０．３３Ｃｏ０．３３Ｍｎ０．３３Ｏ２・Ｍｏ０．０１Ｓｂ０．００５である。
< Comparative Example 3 >
Example 1 except that antimony oxide (Sb 2 O 3 ) was used instead of strontium carbonate, and the antimony oxide was adjusted so that the molar ratio of antimony to the total molar amount of cobalt, nickel, and manganese was 0.005. A positive electrode active material is obtained in the same manner as described above. The composition of the obtained positive electrode active material is Li 1.02 Ni 0.33 Co 0.33 Mn 0.33 O 2 .Mo 0.01 Sb 0.005 as a result of ICP emission spectroscopic analysis.
また、ＣｕＫａ線を使用した粉体Ｘ線回折では、アンチモンのピークは検出されるが、生成物については同定できない。 Further, in powder X-ray diffraction using CuKa line, an antimony peak is detected, but the product cannot be identified.
＜比較例４＞
炭酸ストロンチウムを、コバルト、ニッケル、マンガンのモル総和に対してストロンチウムのモル比が０．０４となるように調整する以外は、実施例１と同様の方法で正極活物質を得る。得られた正極活物質の組成は、ＩＣＰ発光分光分析の結果、Ｌｉ１．０２Ｎｉ０．３３Ｃｏ０．３３Ｍｎ０．３３Ｏ２・Ｍｏ０．０１Ｓｒ０．０４である。
<Comparative Example 4 >
A positive electrode active material is obtained in the same manner as in Example 1 except that strontium carbonate is adjusted so that the molar ratio of strontium to the total molar amount of cobalt, nickel, and manganese is 0.04. The composition of the obtained positive electrode active material is Li 1.02 Ni 0.33 Co 0.33 Mn 0.33 O 2 .Mo 0.01 Sr 0.04 as a result of ICP emission spectroscopic analysis.
また、ＣｕＫａ線を使用した粉体Ｘ線回折からは、ＬｉＳｒ２ＭｏＯ５．５の存在が確認できる。 The presence of LiSr 2 MoO 5.5 can be confirmed from powder X-ray diffraction using CuKa line.
＜比較例５＞
酸化モリブデンのみを混合する以外は、実施例１と同様の方法で正極活物質を作製する。得られた正極活物質の組成は、ＩＣＰ発光分光分析の結果、Ｌｉ１．０２Ｎｉ０．３３Ｃｏ０．３３Ｍｎ０．３３Ｏ２・Ｍｏ０．０１である。
<Comparative Example 5 >
A positive electrode active material is produced in the same manner as in Example 1 except that only molybdenum oxide is mixed. The composition of the obtained positive electrode active material is Li 1.02 Ni 0.33 Co 0.33 Mn 0.33 O 2 .Mo 0.01 as a result of ICP emission spectroscopic analysis.
また、ＣｕＫａ線を使用した粉体Ｘ線回折では、Ｌｉ２ＭｏＯ４の存在が確認できる。 Moreover, the presence of Li 2 MoO 4 can be confirmed by powder X-ray diffraction using CuKa line.
＜比較例６＞
酸化モリブデン、炭酸ストロンチウムの両方を混合しない以外は、実施例１と同様の方法で正極活物質を作製する。得られた正極活物質の組成は、ＩＣＰ発光分光分析の結果、Ｌｉ１．０２Ｎｉ０．３３Ｃｏ０．３３Ｍｎ０．３３Ｏ２である。
<Comparative Example 6 >
A positive electrode active material is produced in the same manner as in Example 1 except that both molybdenum oxide and strontium carbonate are not mixed. The composition of the obtained positive electrode active material is Li 1.02 Ni 0.33 Co 0.33 Mn 0.33 O 2 as a result of ICP emission spectroscopic analysis.
次いで、６０℃で真空乾燥することで、各部材に吸着した水分を除去する。 Subsequently, the moisture adsorbed on each member is removed by vacuum drying at 60 ° C.
ラミネートパック内に、上記非水電解質を注入し、封止することによって、ラミネートタイプの電池を組み立てる。
（４）サイクル特性の評価
上記電池に、微弱電流でエージングを行い、正極及び負極に電解質を十分なじませる。
A laminate type battery is assembled by injecting and sealing the non-aqueous electrolyte into a laminate pack.
(4) Evaluation of cycle characteristics The battery is aged with a weak current so that the electrolyte is sufficiently applied to the positive electrode and the negative electrode.
６０℃に設定した恒温槽内で試験を行う。充電電位４．２Ｖ−充電電流１．０Ｃ（なお、１Ｃは、１時間で放電が終了する電流負荷である。以下、同じ。）、放電電位２．７５Ｖ−放電電流１．０Ｃでサイクル試験を行い、１５０サイクル目の容量維持率を比較する。なお、容量維持率は、１５０サイクル目の放電容量を１サイクル目の放電容量で割った値である。結果を表１に示す。また、実施例１乃至４と比較例１乃至２の結果を用いて、モリブデンの含有量に対するストロンチウムの含有量の比率（モル比）と容量維持率との関係を図１に示す。
（５）サイクル終了後のモリブデンの溶出量評価
１５０サイクル終了後の上記電池から負極を取り出し、取り出した負極から、負極活物質と結着剤と分散剤とからなる負極活物質層を剥ぎ取る。剥ぎ取った負極活物質層を所定量の塩酸で洗浄する。その洗浄液中のモリブデン量をＩＣＰ発光分光分析機で定量する。ＩＣＰ発光分光分析機で測定したモリブデン量を正極活物質層中に含有されるモリブデン量で割った値をモリブデン溶出率とする。モリブデン溶出率が小さい程、電解液へのモリブデンの溶出が少ないことを意味する。結果を表１に示す。
（６）初期放電容量の評価
正極、非水電解質は上記と同様のものを用いる。負極にはリチウム金属を用い、上記ラミネートタイプの電池よりも簡易な電池を作製する。
The test is performed in a thermostat set at 60 ° C. Charging potential 4.2V-charging current 1.0C (where 1C is a current load that completes discharging in 1 hour. The same applies hereinafter), discharging potential 2.75V-cycle current 1.0C. And compare the capacity retention rates at the 150th cycle. The capacity retention rate is a value obtained by dividing the discharge capacity at the 150th cycle by the discharge capacity at the first cycle. The results are shown in Table 1. Further, using the results of Examples 1 to 4 and Comparative Examples 1 to 2, the relationship between the ratio of strontium content to the molybdenum content (molar ratio) and the capacity retention ratio is shown in FIG.
(5) Evaluation of molybdenum elution amount after completion of cycle The negative electrode is taken out from the battery after the end of 150 cycles, and the negative electrode active material layer composed of the negative electrode active material, the binder and the dispersant is peeled off from the taken out negative electrode. The stripped negative electrode active material layer is washed with a predetermined amount of hydrochloric acid. The amount of molybdenum in the cleaning solution is quantified with an ICP emission spectrometer. A value obtained by dividing the amount of molybdenum measured by the ICP emission spectroscopic analyzer by the amount of molybdenum contained in the positive electrode active material layer is defined as a molybdenum elution rate. A smaller molybdenum elution rate means less molybdenum elution into the electrolyte. The results are shown in Table 1.
(6) Evaluation of initial discharge capacity The positive electrode and the nonaqueous electrolyte are the same as described above. Lithium metal is used for the negative electrode, and a simpler battery than the above laminate type battery is manufactured.
２５℃に設定した恒温槽内で試験を行う。充電電位４．３Ｖ−充電電流０．２Ｃで充電した後、放電電位２．７５Ｖ−放電電流０．５Ｃで放電させた時の放電容量を比較する。結果を表１に示す。
（７）エネルギー密度の評価
電池の高容量化のためには、できるだけエネルギー密度の高い正極活物質を用いることが望ましい。そこで、充填性の評価で求めたペレット密度に初期放電容量を掛けた値をエネルギー密度として、比較する。結果を表１に示す。また、実施例１乃至４と比較例１乃至２の結果を用いて、モリブデンの含有量に対するストロンチウムの含有量の比率（モル比）とエネルギー密度との関係を図１に示す。
The test is performed in a thermostat set at 25 ° C. After charging at a charging potential of 4.3 V and a charging current of 0.2 C, the discharge capacities when discharging at a discharging potential of 2.75 V and a discharging current of 0.5 C are compared. The results are shown in Table 1.
(7) Evaluation of energy density In order to increase the capacity of a battery, it is desirable to use a positive electrode active material having as high an energy density as possible. Therefore, the value obtained by multiplying the pellet density obtained in the evaluation of the filling property by the initial discharge capacity is compared as the energy density. The results are shown in Table 1. Further, using the results of Examples 1 to 4 and Comparative Examples 1 and 2, FIG. 1 shows the relationship between the content ratio (molar ratio) of strontium to the molybdenum content and the energy density.
表１から明らかなように、ストロンチウム、タングステン、アンチモンのそれぞれと、モリブデンとを同時に正極活物質に含有させることで、モリブデンのみを含有する場合と比して、モリブデンの溶出率は低減し、サイクル特性が向上している。さらに、充填性において、モリブデンのみを含有する場合と比して、若干低下している実施例もあるが、大幅な低下ではない。 As is apparent from Table 1, by adding each of strontium, tungsten, and antimony and molybdenum to the positive electrode active material at the same time, the elution rate of molybdenum is reduced as compared with the case of containing only molybdenum, and the cycle The characteristics are improved. Furthermore, although there is an example in which the filling property is slightly decreased as compared with the case of containing only molybdenum, it is not a significant decrease.
また、表１から明らかなように、モリブデンとストロンチウムと組み合わせにおいて最もサイクル特性が改善している。モリブデンとストロンチウムとを含有するリチウム遷移金属複合酸化物には、モリブデン−ストロンチウム複合酸化物またはリチウム−モリブデン−ストロンチウム複合酸化物或いはそれらの混合体が存在している。実際に、ＣｕＫα線を使用した粉末Ｘ線回折の結果からは、ＳｒＭｏＯ４、ＬｉＳｒ２ＭｏＯ５．５が確認される。これに対して、タングステン、アンチモンの場合、粉末Ｘ線回折によって、生成物は確認されていない。このことから、ストロンチウムは、モリブデンと結合して化合物を形成しやすい元素であり、タングステン、アンチモンの場合と比較して、電解液に溶出しやすいモリブデン酸リチウムの生成を抑えることができると考えられる。さらに、生成した上記複合酸化物は、電解液に対して比較的安定な化合物であるため、複合酸化物自体も電解液への溶出が小さいと考えられる。したがって、モリブデンとストロンチウムとの組み合わせは、モリブデンの電解液への溶出を最も抑えることができ、サイクル特性が大幅に改善される。 Further, as apparent from Table 1, the cycle characteristics are most improved in the combination of molybdenum and strontium. The lithium transition metal composite oxide containing molybdenum and strontium includes molybdenum-strontium composite oxide, lithium-molybdenum-strontium composite oxide, or a mixture thereof. Actually, SrMoO 4 and LiSr 2 MoO 5.5 are confirmed from the results of powder X-ray diffraction using CuKα rays. On the other hand, in the case of tungsten and antimony, no product has been confirmed by powder X-ray diffraction. From this, strontium is an element that easily forms a compound by combining with molybdenum, and it is considered that the formation of lithium molybdate that easily elutes into the electrolyte solution can be suppressed as compared with tungsten and antimony. . Furthermore, since the produced composite oxide is a compound that is relatively stable with respect to the electrolytic solution, the composite oxide itself is considered to have a small elution into the electrolytic solution. Therefore, the combination of molybdenum and strontium can minimize the elution of molybdenum into the electrolyte, and the cycle characteristics are greatly improved.
また、モリブデンの含有量に対してストロンチウムの含有量を変化させた場合、図１から明らかなように、ストロンチウム／モリブデン（モル比）が０．５以上になるとサイクル特性の向上が顕著である。しかし、ストロンチウムの含有量が増えるにつれて、充填性と初期充放電容量とが低下し、結果としてエネルギー密度が低下する。したがって、電池の高容量化のためには、ストロンチウム／モリブデン（モル比）が、０．５〜２．０の範囲の正極活物質を用いることが好ましい。 Further, when the content of strontium is changed with respect to the content of molybdenum, as is apparent from FIG. 1, when the strontium / molybdenum (molar ratio) is 0.5 or more, the cycle characteristics are remarkably improved. However, as the strontium content increases, the filling property and the initial charge / discharge capacity decrease, and as a result, the energy density decreases. Therefore, in order to increase the capacity of the battery, it is preferable to use a positive electrode active material having a strontium / molybdenum (molar ratio) in the range of 0.5 to 2.0.
上述したように、タングステン、アンチモンは、ストロンチウムと比較すると、サイクル特性は若干劣るが、モリブデンの含有量に対して上記元素の含有量を変化させた場合、図１に示すストロンチウムと同様の傾向となると考えられる。したがって、モリブデンの含有量に対する上記元素の含有量の比率は、ストロンチウムと同様に、モル比で、０．５〜２．０の範囲であることが好ましい。 As described above, the cycle characteristics of tungsten and antimony are slightly inferior to those of strontium, but when the content of the above elements is changed with respect to the content of molybdenum, the same tendency as that of strontium shown in FIG. It is considered to be. Therefore, the ratio of the content of the element to the content of molybdenum is preferably in the range of 0.5 to 2.0 in terms of molar ratio as in the case of strontium.
本発明の非水電解質電池用正極活物質は、非水電解質電池に利用することができる。 The positive electrode active material for a non-aqueous electrolyte battery of the present invention can be used for a non-aqueous electrolyte battery.
本発明の非水電解質電池は、携帯電話、ノート型パソコン、デジタルカメラ等のモバイル機器及び電気自動車用バッテリー等の電源に利用することができる。
The nonaqueous electrolyte battery of the present invention can be used as a power source for mobile devices such as mobile phones, notebook computers, digital cameras, and batteries for electric vehicles.
Claims (2)
前記正極活物質は、少なくともニッケルとコバルトとマンガンとを含有し、層状構造を有するリチウム遷移金属複合酸化物であって、
前記リチウム遷移金属複合酸化物は、ストロンチウムと、モリブデンと、を含有し、
前記モリブデンの含有量は、前記リチウム遷移金属複合酸化物に対して、０．１ｍｏｌ％以上１．５ｍｏｌ％以下であり、前記モリブデンの含有量に対する前記ストロンチウムの含有量の比率は、モル比で、０．５以上２．０以下であることを特徴とする正極活物質。 In the positive electrode active material used for the nonaqueous electrolyte battery,
The positive electrode active material contains at least nickel, cobalt, and manganese, and is a lithium transition metal composite oxide having a layered structure,
The lithium transition metal composite oxide contains a strontium arm, and molybdenum, and
The molybdenum content is 0.1 mol% or more and 1.5 mol% or less with respect to the lithium transition metal composite oxide , and the ratio of the strontium content to the molybdenum content is a molar ratio. positive electrode active material of der Rukoto wherein 0.5 to 2.0.
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